Table ii



, M y 5 V 'R. R.'SODEN EI'AL 3,183,193 omen. mssn CRYSTALS Filed Aug. v, 1961 FIG. I

FIG. 2

RELATIVE EMISSION INTENSITY I; l I

lo" :0" I0" I 0.5 o LOGARITHM OF EUROPIUM CONCENTRATION R. R. 5005 INVENTORS'L. a. ww U/TERT jm w/ 2 i tom levels;

, 3,183,193 OPTICAL MASER CRYSTALS Uitert, MorrisTownship, Morris County, N.J., assignors to 3 Bell Telephone Laboratories, incorporated, New York,N.Y., a corporation of New York p Filed Aug 7, 1961, Ser. No..129, 797

f 3Claims. (CI. 252-301-5) Thisinvention relates to single crystal tungstate and molybdate materials exhibiting fluorescent properties and to devices utilizing such crystals.

Recently, considerable interest has developed in a new Ralph R.'Soden, Scotch Plains, and Le Grand G. Van

class of solid state maserdievices in which the stimulated frequency is in the optical or near optical spectrum including the infrared and ultraviolet portions of the electromagnetic spectrum. .This spectrum encompasses the wavelength range of from 100 A. to 2X10 A. In principle, these devices are directly analogous to the microwave maser, and the mechanics of their operation are well detailed in the literature, for example as'descr ibed by A. L.

" Schawlow and C. H. Townes in U .S. Patent 2,929,922,

issued March 22, 1960. Among the more promising forms of optical masers are those which employ a material whose energy level system is characterized by at least three energy levels, with the separation of these levels falling within the desired operat- -ing frequency ranges. During operation, there is established, at leastjintermittently', a nonequilibrium electron population distribution in a pair'of the selected three energylcvels. In particular, the population of the higher of the selected. pairs'of energyleyels'is increased to the point at which it is greater than that of the lower level. It

is customary to refer to a material in such a state of nonequilibrium as exhibiting a negative temperature.

It is characteristic that if there is applied to a material in a negative temperature state a signal of a frequency which satisfies .Planck's Law with respect to the two ene'rgy levels in nonequilibrium, the applied signal will stimulate the .emission of 'radiation in phase-with the signal frequency from the material and the signal will be amplified. In other words, the active maser material is chosen such that. the two energy levels are separated by an. energy equal to ha, where h is Plancks constant and a is equal to the frequency to be amplified. This separa tion is less thanthe separation between'the top and bottom levels of the selected three-level energy system.

The negative temperature state is established by applying tolthe material pump energy of a frequency of. at least the frequency corresponding to the separation be- .tween the top and bottomlevels of the selected three-level energy system. The application of sufiicient pump energy affects electron transitions from the bottom level tothe Patented May it, 1965 quency, the emission line preferably corresponds to a transition to a state other than theground state such that the single bright emission line is narrow in width.

Since the pump sources typically utilized in optical masers generally exhibitan energy output over abroad frequency spectrum, it is desirable, that the paramagnetic ions possess a broad absorption spectrumtofacilitate es tablishment of the negative temperature state. Desirably the paramagnetic ions also exhibit a relaxation time sufficiently long so that the quantum etficiency for fluorescence is close to unity. Otherwise, the magnitude of the pumping frequency would have to be greatly increased in order to maintain a negative temperature state wherein 'sufiicient electrons are available in the higher energy level to amplify the input frequency. To ensure a narrow emission line, the energy level widths of the pair of spaced energy levels in the negative temperature state are preferably narrow.

In view of the above-detailed requirements, very few optical maser materials are known to the art. Most published work on optical masers is directed to ruby crystals and calcium fluoride crystals containing small amounts of uranium (III) and samarium (II). Ruby crystals, however, suifer the disadvantage of requiring high pumping power to establish a negative temperature state. As such under the usual conditions ruby masers are limited .in,

operationto producing a pulsed beam of coherent light.

toplevel and the populations of the bottom and top levels I are thereby made to approach equality. Underthese conditionstherewill bea'negative temperatureeither between the top and' middle levels or betweenthe'middle and bot-' :.-.Since, acompeting process known as relaxation tends tov return the system to equilibrium, thereby destroying negative] temperature state; continuous pump energy-is 'appliedto the material during theperiod of signal amplification. 1

Among the more promising active maser materialsare those which comprise a host crystal containing paramagnetie ions from which the stimulated emission occurs. The host crystal of amaterial meeting the above-described requirements must be capable of accepting the paramagnetic ions in such a way that they are able on excitation to fiuores'ce with good over-all quantum efiiciency, with as much of the emitted energy as possible concentrated. in a single'line. To maximize amplification of the signal fre- As pveviouslydiscussed, there should be acor'respondy ence between the signal to be amplified andthe energy level separations of the maser material. Therefore, it is, desirable that new maser materials having a range of energy level separations and fulfilling the above-detailed requirements be developed so'that a range of signal fre-.

quencies can be amplified.

In accordance with the invention, new fluorescent compositions of matter suitable for use in optical maser devices have been developed. The host lattices of these compositions are rubidium-terbium tungstate, rubidiumterbium molybdate and cesium-terbium molybdat'e in which restricted. amounts of the terbium atoms have been replaced witheuropium in the 3+ valencestate. The

compositions have the empirical formula as os-x x where A is selected from thegroup consisting of rubidium and cesium, B is selectedfrom the group consisting of W0 and M00 but when A is cesium, B must be M00 and x has a value of from 0.001 to 0.40. The subscripts in the above formulae signify the relative number of gram atoms of the element indicated which are present and number of atoms thus are also proportional to the relative of each element present in the composition.

The compositions of the invention emit energy of 4 narrow line width. For example, the line width of Rb Tb Eu' WO 'associated with an emitting wave:

length of approximately 6,l50 A.-is in the orderIof 2.5.- cm.- at liquid nitrogen temperature. The excited electrons evidence a relaxation. time sufficiently long so that 6' the quantum efficiency for fluorescence is close to unity.

Since the ions possess at least three energy levels and electron transitions .are to other than the ground state, the

establishment of a-continuous negative temperature state is feasible and the material is capable of fluorescing in a continuous beam of coherent light.

The invention may be more easily understood by reference to the drawing, in which: i

FIG. 1 is a front elevational view of an apparatus utilizing the compositions of the invetion; and

FIG. 2, on coordinates of relative emission intensity and I gramatoms per formula of trivalent europium ion,;is a

semi-log plot showing the dependency of the emission intensity on the concentration of europium ion in the Compositions of the invention.

Referring more, particularly to FIG. 1, there is shown a rod shaped crystal 1 having the composition as disclosed lieicin. Pumping energy is supplied by means of helical lamp 2 encompassing rod 1 and connected to an energy source not shown. having a compact. arc of high pressure mercury. Ends 3 and 4 of rod l are ground and polished so as to be optically'llat and parallel and are silvered so as to pro phcre of liquid nitrogen (at a temperature of approximately 79 K.) so as to more readily attain a negative '-temp,erature state.

The spectrum ofthe pump source including ultraviolet light is desirably within the range f 2,000 A. to 4,200 A.

Although higher frequencies are suitable, sources of such frequencies are not generally available. It has been found Ten micron slit widths were employed at the entrance and exit to the spectrometer. The system was calibrated against a tungsten filament lamp, whose output was as- ].amp 2 is an ultraviolet lamp I that ultraviolet light having a peak of 3,660 A. is most advantageous for the present purposes.

Although the expressed range is in the range of. energy most elTective, it, is not necessaryto use a source having an output restricted to this range. For example, a gaseous discharge flash bulb. although emitting white light, never- 1 thelessemits a large amount of. energy in the desired spectrum.

Device discussion has been largely in terms of the most commonly reported maser design. Although such a device. is easily fabricatethother conligurations have been disclosed in the literature and may prove advantageous. 'All such variations are considered to be within the scope of the invention.

The client of europium ion concentration on the emission intensity of the compositions ofthe invention is shown in FIG. 2. in this figure. the ordinate measures the relative emission intensity of several tungstate compositions containing added europium and having the formula Rb Tb Eu WO with the abscissa indicating the logarithm of the europium content ofthese compositions.

It has been found that replacing W0 in the rubidium tungstate compositions of the invention with M00 results in',rubidium-molybdate compositions having comparable line widths and somewhat higher emission intensities than thetun'gstate composition. It has further been found that cesium m-olybdates of the formula Cs Tb Eu MoO exhibit line widths and intensities comparable to the of 0.40 is governed by maser operation and efficiency.

Beyond this limit interaction between the rare earth ions results in a decrease in amplification. As seen from the figure, increasing amounts of rare earth ion inclusions above the minimum limit-of 0.001 causes the emission intensity to pass through a maximum and then decrease. Based on the preceding considerations, a preferred europium ioninclusion range is 0.004 to 0.20 gram atom per formulawith an optimum range being 0.01 to 0.10 gram atom per formula.

' To obtain curves 1 and 2 of FIG. 2, measurements were made on various materials of the present invention with a (Tie'rtner'high dispersion spectrometer adapted with an AMINCO photomultiplierusing a IP22 tube.

sumcd to have a black-body dependence, to give relative values of brightness of the emitting surface in units of powerpcr unit wavelength range. Emission was excited by illuminating a sample one inch long by one-half inch wide by one-quarter inch deep with a 3.660 A. rich 1-]. spotlamp through a Corning 5874 filter. The measurcments on the tungstate crystals of the instant invention were made at room temperature, and the measurements on the molybdate crystals of the instant invention were made at liquid nitrogen temperature. The intensities are relative to 100 for the 6,150 A. peak of a comparable sample of Na Eu WO.,.

As evidenced by FIG. 2, the substitution of rubidium for sodium in the sodium-europium tungstate structure results in a composition having one-third the emission intensity of sodium-europium tungstate. However, the rubidium-europium tungstate structure exhibits a line width approximately one-third that of sodium-europium tungstate. In sodium-europium tungstate the sodium and europium ions are randomly distributed in equivalent sites. The resulting random electrostatic field of the disordered structure causes line broadening. In rubidium-europium tungstate the rubidium and europium ions are located in nonequivalent sites, thereby resulting in an ordered structure having a uniform internal electrostatic field which permits narrow line width.

'As further evidenced by curve 1 of biumion dilutions of the rubidium-europium tungstate structure enhance the emission intensity of this structure. The peak emission intensity of the resultingstructure approximates the emission intensity of the sodium-europium tungstate structure.

It has been determined that replacing tcrbium with other rare earth ions in the tungstate and molybdatc compositions of the invention results in either a nonfluorescent or weakly fluorescent material. For example, 'the substitution of cerium for terbium results'in a nonfiucrescent material, while the substitution of dysprosium, erbium, holmium, thulium, and other rare earth ions results in only a weakly fluorescent material.

composition. It has been determined that the other rubidium tungstate compositions of the invention exhibit similar D spacings and emission intensities. Table III sets forth the calculated D spacing and emission intensity for the Cs 'I'b Eu Mo0 composition. It has been determined that the other cesium molybdate compositions of the invention exhibit similar D spacings and cmission intensities. In these tables, the emission intensities are defined as follows:

Tr.=trace VVW=very, very weak V.VVw vcry, very, very weak VW=very weak =mediurn S =strong MS=medium strong MW=medium weal:

this figure, ter- I 9. 4. 3. 3. 3. 3. 3. 3. 2. 2.48 Tr. 2.38.. W VW 2.36 2.27 2.04 2.01 1.96 1.89 1 84 1 78 1.75

TABLE II D spacings Int. D spacings Int.

.83 M 1.63 V V V W .14. VW 1.61. VVVW .45. W 1.58- W .12. VW 1.56; VVW .87. WW 1.52- .38 1S, V 1.51. VVVW .22- (W 1.49. .11- M 1.47- .06. .VW 1.46- .97- M 1.44- .82. VW 1.42- Tr. .72 VVW 1.39- V V V W .58. MW 1.37- VVVW .52--..- VVVW 1.36- .47 VW 1.35- .39- VVW 1.31 .30. Tr. 1.30. .25 V V VW 1.28- .22- VVW 1.27- VVVW .18. VVVW 1.26- V V VW .15 Tr. 1.25- .05 Ti. 1.24 .00 VVVW 1.23. .98 VVW 1.21- .90 w 1.20-

.79 W 1.19 VV VW .78 VW 1.183 W .76. VW 1.157 V .69. .MS 1.149 .64. ,VVVW

TABLE III The tungstate crystals of the instant invention are advantageously grown by the ditungstate flux method disclosed in patent 3,003,112, issued October 3, 1961 to L. G. Van Uitert. Briefly, in accordance with this method, a mixture of the desired tungstate and a europium containing composition is heated in suitable alkali metal ditungstate flux to a temperature sufiicient to form a molten solution. The flux, which is a solvent for the tungstate and the europium containing composition, may contain an excess of tungstic anhydride in a molar amount up to the amount of the tungstate present in the initial mixture to enhance the solubility of these components.

' The moltensolution is then slowly cooled until it solidifies."

In the course of cooling, crystals of the tungstate containing europium ions are formed in the flux.

A comparable procedure is employed to grow the molybdate crystals of the invention by means of a dimolybdate flux optionally containing an excess of molyb dic anhydride.

' to qunchthe fluorescence of other rare earth ions in the. I

i per'atures', from being reduceitp ajlowef valency state.

The initial mixture is equivalent to 10 mol parts to mol parts of the tungstate or molybdate and mol parts to 25 mol parts ofthe flux. One advantage of the flux is its solvent power, which permits temperatures of 900 C. to 1,450 C. for the ditungstate flux and 900 C. to 1,250 C. for the dimolybdate flux to be used informing a molten solution of the mixture. These temperatures avoid reduction of the europium ionsto lower undesirable valency states which are not suitable for optical maser use. Additionally, loss of tungstic or molybdic anhydride is not appreciable at these temperatures.

There is no critical limitation to particle size ofrthe initial ingredients since a molten solution is formed of the initial mixture. However, .it desirable 'to minimize the amount of accidentally ad ed rare earthion impurity in order to insureconsistent results. For example, the presence of a fraction of a percent of cerium is sufficient tungstates or molybdates. With the exception of cerium,

however, accidentally added rare earth'ion impurities are.

earthion intentionally added. To minimize such con- 1 tamination, spectroscopically pure rare earth substances, such as oxides, are typically utilized in the initial mixture. Generally, the non-active ion impurity limits are not critical and ordinary reagent grade tungstates or molybdates or substances that react to form the tungstates or molybdates are utilized.

The atmosphere in which the initial mixture is heated is not critical. However, it is well known to use an oxygen-containing atmosphere such as air, oxygen or oxygen plus an inert gas to prevent an ion in a higher valency state such as europium, which is unstable at elevated tem- Similai'ly, for convenience, atmospheric pressure is normal-FyTTsedTahhough pressure is notcritical; 'As isiwell.-. known, increased pressures in general enhancesolubility of the solute, "thereby permitting lower temperatures to be used.

After the heating step, the molten solution is cooled at a controlled rate of 0.1" C./hr. to 25 C./hr. in the same atmosphere used in the heating step until it solidifies, forming tungstate or molybdate crystals having fluorescent curopium ions dispersed therein. 'The solidification point is readily determined visually. For most of the molten solutions, cooling to a temperature of 650 to 850 C. is adequate to cause solidification.

The tungstate or molybdate crystals in the flux are then furnace-cooled or quenched to room temperature. The 3 ditungstate flux is removed from the tungstate crystals by washing the crystals with an alkali such as a solution of sodium hydroxide. The dimolybdate flux is removed from the molybdate crystals by washing the crystals with water.

Specific examples of procedures utilized in preparation of compositions of the invention are given below. In all cases the properties of the resulting compositions were measured as previously described and the measurements plotted in accordance with the description in conjunction with FIG. 2. These examples are to be construed as illustrative only and not as limiting in any way the scope and spirit of the invention.

Example 1 122.5 grams Rb CO 15.4 grams Tb O 3.7 grams B11303, and 276.2 grams W0 were dry mixed together.

The mixture was then heated in a platinum crucible in air i position:

. 7 of 25 C. per hour to a temperature of 700 C. The resulting solids where then furnace-cooled to room temperature and washed with hot sodium hydroxide, leaving rubidium-terbium tungstate crystals doped with trivalent europium. The formed crystals had the following como.5 o.4 o.1 4 Example 2 122.5 grams Rb CO 18.48 grams Tb O 0.74 gram Eu O and 276.2 grams W0 were dry mixed. The mixture then underwent the same processing as detailed above, with the resulting formation of rubidium-terbium tungstate crystals doped with trivalent europium. The formed crystals had the following composition:

Example 3 122.5 grams Rb CO 18.48 grams Tb O 0.74 gram Eu O and 171.7 grams M00 were dry mixed. The mixture then underwent the same processing as detailed above, with the resulting formation of rubidium-terbium molybdate crystals doped with trivalent europium. The formed crystals had the following composition:

8 Example 5 66.07 grams Cs cO 5.15 grams Tb,o,, 0.551 gram Eu O and 63.0 grams M00 were dry mixed. The mixture then underwent the same processing as detailed above, with the resulting formation of cesium-terbium-europium molybdate crystals doped with trivalent europium. The formed crystals had the following composition:

What is claimed is: 1. A composition. of matter having the empirical formula where A is selected from the group consisting of rubidium and cesium, B is selected from the group consisting of WQ and M00 but when A is cesium, B must be M00 and x has a value of from 0.001 to 0.40. 2. A composition of matter in accordance with claim 1 wherein x has a value of from 0.004 to 0.20.

3. A composition of matter in accordance with claim 1 wherein x has a value of from 0.01 to 0.10.

References Cited, by' the Examiner UNITED STATES PATENTS 2,929,922 3/60 Schwalow et a1. "-2 88-61 OTHER REFERENCES Kroger: Some Aspects of the Luminescence of Solids,

Elsevier Pub. Co., Inc., New York, 1948, pages 109, 110, 291, and 297. Y

MAURICE A. BRINDISI, Primary Examiner.

JOSEPH R. LIBERMAN, Examiner. 

1. A COMPOSITION OF MATTER HAVING THE EMPIRICAL FORMULA 